Aziridine-methylolphosphorus polymers and flame resistant organic textiles



United tates Patent 2,886,539 AZIRIDINE-METHYLOLPHOSPHORUS POLY- MERS. AND FLAME RESISTANT ORGANIC TEXTILES George- L. Drake, Jr., Wilson A. Reeves, and Leon H. Chance, New Orleans, La., assignors to the United "States of-Americaas represented by the Secretary of Agriculture No Drawing. Application June 5, 1956 Serial No. 589,562

12 Claims. (Cl. 260-2) (Grantedlunder Title 35, US. Code (1952), see. 266) A non-exclusive, irrevocable,.royalty-free license in the invention herein described, throughout the' world for all purposes of'the United States Government, with the" power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to new phosphorus and nitrogen containing polymers, processes fortheir production and processes of employing these polymers in the flameproofing pf certain organic fibrous materials.

In general, this invention relates to polymers capable of being produced by the reaction of a l-aziridinyl phosphine oxide orsulfide (e.g. a compound that contains at least one l-aziridinyl group,

attached to pentavalent phosphorus), with a methylol phosphorus compound of the formula wherein Arepresents .a monovalent anion and R represents OH or a radical produced by the reaction of the OH ofa PCHQOH group with anitrogen compound containingat least one trivalent nitrogen atom and at least one member selected from the group consisting of H and processes ofreducing the combustibility of hydrophilic fibrousorganic materials. Methods for producing reac tionproducts .of the methylol phosphorus compoundswith the trivalent nitrogen compounds are disclosed in Patent Numbers 2,772,188, 2,809,941, and 2,812,311.

Oher aziridinyl compounds that undergo reactions described herein consist of compounds or polymers containing-the: following structures:

a diallrylamine, :an alkyl, an alkylene or an'ar-yl group; M isboron, phosphorus, sulfur,- arsenic, carbon,'silicon',

CH QH attached to trivalent nitrogen atoms; and the 2,886,539 Patented May 12, 1959 ice 2 antimony or titanium; Some typical examples ofcoin pounds and polymers are:

iomo'n N r13, 0112011251 s10, 'onaonm so2 (to). (Q (1m).

We have discovered that compounds'that contain at least .one l-aziridinyl group attached to pentavalent phos phorus atoms react with methylol phosphorus compounds (e.g. compounds that contain at least. two HOCH P groups) to produce polymers. Such polymers contain the reoccurring connecting structures,

r -l r-on -onrr r-r, P1 I-'-o1rr-P' and- 1= c'H, 0m-0 ;H, P wherein the phosphorus atoms are pentavalent.

Such polymers can be produced in the form of solid synthetic resins. They'can bedeposited on the surfaces and/ or in the interstices of hydrophilic fibrous organic materials, i.e., organic materials which absorb or adsorbwater. When such resins are deposited, they reduce the combustibility of hydrophilic'fibrous organic materials and resist removal by laundering-and the like chemical treatments. Such resins can be deposited on the surfaces of non-hydrophilic materials to form fiame resistant coat ings.

l-aziridinyl-phosphine oxides or sulfides suitable for use in this-invention are compounds which contain at least one l-aziridinyl group, (CH N-, attached to pentavalent phosphorus atoms; The compounds used in this invention may be represented by the following structure:

Reacting? compound (i.e. a compound capable of react-' ing with a PCH OH group) to produce a derivative that retains at least two PCH 'OH groups. The phosphoniurn chloride, tetrakis(hydroxymethyl)phosphonium chloride,

of the formula (HOCH PC1-, is a readily obtainable phosphoniurn'salt, and is the preferred salt for'employmentin the present process. However, by the usual procedures'for replacing-theanionof such an oniumsalt, the

phosphonium chloride can readily be converted to, and employed in the form of, for example: the phosphonium acetate (HOCH POAc; the phosphonium dihydrogen phosphate O (HO OHahPO ZQOH):

or the like phosphonium salt. The methylol phosphorus group containing derivatives of the phosphine oxide or the phosphonium salt can be a substantially monomeric product of reacting the phosphorus compound with at least one methylol reacting compound which is monofunctional in its capacity to react with PCHgOH groups, so that from about 1 to 2 moles of the methylol reactingcompound combines with each mole of the phosphorus compund. Illustrative examples include the products of so reacting the tris (hydroxymethyl) phosphine oxide and/ or the phosphonium salt with at least one: secondary amines such as diethylamine, N-vinyl cyclohexylamine, or the like; N-substituted amides such'as N-methyl acrylamide, N-N-trimethy1 pinic acid diamide, N-propyl benzamide and the like; acids such as stearic acid, pinonic acid, monobutyl phthalate, and the like; and the like monofunctional reactants. The methylol phosphorus containing derivative can be a further polymerizable methylol phosphorus polymer such as water soluble polymers formed by reacting tetrakis(hydroxymethyl) phosphonium chloride with melamine or with methylated methylolmelamine such as those described in copending patent application Serial No. 421,213, filed April 5, 1954, now Patent No. 2,812,311.

Polymers provided by this invention can be produced in acidic, neutral, and alkaline conditions. vThey can be produced in the form of liquids or solids and can be molded by the conventional techniques of molding thermosetting resins. These polymers are valuable materials for use in production of: molded synthetic articles, such as buttons, electrical insulators and the like; synthetic coatings such as protective coatings, and paints and the like having reduced flammability; paper treating resins; textile resins; and the like.

The polymers provided by this invention are preferably prepared by gently heating a solution of the aziridinyl phosphine oxide or sulfide and the methylol phosphonium or methylol phosphine oxide until polymerization occurs. The preferred relative amounts of aziridinyl compound and methylol phosphonium or phosphine oxide used to polymerize can be calculated by conventional methods by assuming that: 1) for each aziridinyl group present in the compound, the functionality is two (e.g. if two aziridinyl groups are present, the functionality is four), (2) that the functionality of the methylol phosphorus compound is equal to the number of methylol groups present in the compound, (3) that tetrakis(hydrxymethyl)phosphonium chloride is converted to tris(hydroxymethyl)phosphine oxide in the presence of neutral carbonates like calcium carbonate, alkali carbonates like sodium carbonate, alkali metal hydroxides, tertiary amines, and bases in general. Thus it is apparent that, in the preferred relative proportions, the azirdinyl compound and the methylol phosphorus compound will be present in such amounts that one aziridinyl group is provided for two methylol groups.

The polymers of this invention can be modified by incorporating an alkyl amine or an aliphatic alcohol into the solution containing the aziridinyl compound and the methylol phosphorus compound. For example if cetyl alcohol is used the polymers are especially suited for use in the production of soft, flame-resistant textiles.

The combustibility of organic fibrous materials can be reduced in accordance with this invention by: impregnating the fibrous materials with an aqueous solution, or uniform suspension or dispersion, of the monomeric com pounds, or the partially polymerized monomers formed.

compounds until partial polymerization occurs; and curing the impregnated materials 'at the temperatures conventionally used for curing fibrous organic materials.

When tetrakis(hydroxymethyl)phosphonium chloride is the methylol phosphorus compound used, it is preferable to dissolve it in water first, then add sulflcient basic reacting compound to raise the pH of the aqueous solution to about 5 to 7 before adding the aziridinyl compound.

The pH of the solution containing the methylol phosphorus compound and the aziridinyl compound greatly influences the nature of the resulting polymer. The pH of these solutions can be adjusted with substantially any acid or base reacting material. Suitable acids include hydrochloric and acetic. Suitable bases include sodium hydroxide, sodium bicarbonate, sodium carbonate, triethanolamine and ethanolamine. If the pH of the solution is less than about 5.5, polymerization often proceeds so rapidly when heated that sufiicient heat is produced from the exothermic reaction to cause the product to decompose with evolution of white fumes. The preferred pH of the solution is from about 6 to 8. A much higher pH can be used.

Surface active agents, water repellents, and other textile treating agents may be incorporated into the aqueous or emulsion treating media to modify the treated textiles.

Surface active softening agents improve tear strength of cotton and rayon fabrics. v

The process of this invention can suitably be used to reduce the combustibility of substantially any hydrophilic fibrous material such as cotton, rayon such as viscose rayon, ramie, jute, wool, paper, carboard and the like materials which can be impregnated with a liquid and dried or cured.

Where a textile is being impregnated, it is of advantage to remove excess impregnating liquor by passing the textile through squeeze rolls prior to drying or curing the impregnated textile. It is also advantageous to dry the textile at about 70 to C. before it is cured at a temperature of from about 100 to C. V

The degree of flame resistance imparted to a textile by these phosphorus and nitrogen containing resins can be varied from a low degree to a very high degree by varying the amount of polymer put in the textile.

Some advantages of flameproofing textiles in accordance with this invention are: textiles treated by this process are flame resistant, glow resistant, shrink resistant, and rot and mildew resistant; the effects of the treatment are permanent, and resistant to laundering, dry cleaning, and boiling alkali solutions; cellulosic textile materials retain a very high percentage of their tear and tensile strength; the treated cellulosic materials are resistant to the influences of hypochlorite bleaching as determined by tensile strength; treated textiles are made highly flame resistant with relatively small amounts of these phosphorus and nitrogen containing polymers.

In the examples provided below the following test meth ods were used to demonstrate flame resistance of fabrics provided by this invention:

(1) The vertical flame test as described in US. Federal Service, Federal Specification CCC-T-191b (1951). In this test, a strip of cloth is exposed to the luminous flame of a Bunsen burner and flameproofness is judged by the length of a tear produced through the charred area by a standard weight. The results of this test are expressed in char length in inches.

(2) The strip flame test as described in Textile Research Journal, volume 23, page 529 (1953). In this test, the degree of flame resistance is measured by determining the angle at which a narrow strip of cloth will not continue to burn when held in the vertical position and ignited at the bottom and then slowly rotating the cloth until the flames goes out. The greater the angle at which theflame goes, Out the greater the degree of flame re- 31.. sistance. 180 degrees respresents the highest degree of flame resistance.

EXAM PLE, 1

An aqueous solution was madeby dissolving-Smarts divided into four equal parts (A, B, C, and D) andtreated A was allowed to remain at pH as described below. 5.1. The pH of B, C and D was adjusted with triethanolamine to 6.1, 7.1 and 7.9 respectively. Some of each solution, A, B, C, and D was plaeedin awateh glass and then placed upon a steam bath for minutes. At this time sample D was a hard clear-mass, C was a toughmass and samples A and B were very viscous liquids. After an additional 15 minutes on the steam bath samples B, C and D were hard polymers whereasA was a very tough mass.

Samples A, B, C, and D (previouslyheated for 30 minutes on steam bath) were placecl in- ;oyen at 140 C. for 5 minutes. Polymer A was light brown and water soluble. B was yellowish brown and-was insoluble in water and acetone. Polymers C and D were also insolublein water and in acetone and were light yellow in-color. All samples were highly flame resistantandcontainedphosphorus, sulfur and nitrogen.

EXAMPLE 2 An aqueous solution was made containing 2.5. parts of tris(1-aziridinyl)-phosphine sulfide, 2.5 parts ,of tris(hydroxymethyl)phosphine oxide and parts ofwater. The pH. of the solution was 5 .1. It was dividedinto two equal parts, A and B and then partB wasadjusted to apHv of 9.0 with triethanolamine. placed upon a watch glass and heated on steam cone for 90 minutes. Viscous colorless polymers formed in both cases. They were then heated for 5 minutes at 140 C. Light yellow tough polymers formed that were insoluble in water and in ethanol.

When some of solutions A and B were placed directly in an oven at 140 0., without prior heating on the steam bath, sample A decomposed with the formation of'dense white fumes.

EXAMPLE 3 An aqueous solution was made containing 6- parts of tris(1-aziridinyl)phospbine oxide, 4.8 parts of tris(hydroxymethyl)phosphine oxide and 43 parts ofwater and then sufficient sodium carbonate was added to raise the pH to 8.2. Most of the water was evaporated under reduced pressure and then the viscous liquid was heated on steam bath for 100 minutes. The product became insoluble in boiling water. The resulting material was heated for minutes at 110 C. in oven to produce a hard, clear polymer. It was pulverized and washed with water and then with acetone. The washed polymer contained phosphorus and nitrogen an d was flame resistant.

EXAMPLE, 4

A cotton cloth was wet-out in an aqueous solution containing 10% tris(1-aziridinyl)phosphine sulfide, 10% tetrakis(hydroxymethyl)phosphoniurn chloride, 2% triethanolamine and 4% rnethylolrnelamine. The cloth was dried and then heated 3 minutes at 160- C. After heating, it was washed in hot water and dried. The clothwas strong, it had a good hand, contained. sulfur, phosphorus and nitrogen. The cloth was highly flame resistant.

EXAMPLE '5 An aqueous solution with apH of 6.0-6.5--was prepared containing 12.5% tris(1-aziridinyl)phosphine oxide, 12.5% tetrakis(hydroxymethyl)phosphoniurn chloride, 4.0% triethanolamine and 1.5% cationicsoftener. The solution was applied to 8.2 oz. cotton twill; i n,a;p adder to a W p r p o r h aht .wasrdriedrie A part of each sample was in "Table-I below. The treated fabric was not onlyflarneresistant but also" glow resistant.

Table. I

Tear Breaking Char Length I Strength Strength (inches) Curing Temp, Resin Elmendorf Strip 0. Add-on, (warp) (warp) I Percent Strength Strength Before After retained, retained, soap soap Percent Percent boll boil 6. 7 180 89 4. 4 I BEL, 8. 8 160 86 4.1 BEL. I 10. 2 155 88 3. 9 4'. 6

I 1 Strength retained is based upon an untreated controlfabric.

9 BEL means that thestrip burned entlre'length.

As shown in Table I the products showed excellent flame-resistance with as low as 6.7% resin add-on. Samshowed excellentflame resistance and no afterglow after the strenuous three-hour soap boil previously described. The hand and appearance of the fabric was substantially unaltered by the resin treatment.

EXAMPLE 6 Another sampleof 8 oz. cotton twill was treatedas 1 described in Example 5 except that the treating solution,-

test method. It had an excellent handle and was highly flame andglow resistant.

EXAMPLE 7 8 oz. cotton twill was treated as described in Example 6 except that the treating solution'contained 4% triethanolamine, 20% tris(1-aziridinyl)phosphine oxide and. 20% tetrakis(hydroxymethyl)phosphonium chloride. The treated fabric contained 22.6% resin after drying, curing and washing and had a char length of 2.8 inches.

EXAMPLE 8 A'treating solution was prepared containing the same amounts of reagents as in Example 7 above and in addition it contained 0.4%of a wetting agent. Five different fabricsviscose rayon, fortisan, a cotton-fortisan-blend, acotton-nylon blend and a cotton-viscose rayon blendwere padded in the solution, dried at about 75 C. then cured at 140 C. for about 5 minutes. After washing and again drying, the fabric were all highly flame resistant and contained phosphorus and nitrogen.

EXAMPLE 9 8.2 oz. cotton fabric was padded through an-aqueous solution (pH of 5.9) containing 16% tris(l-aziridinyl) phosphine sulfide, [(CH N] P=S, 16% tetrakis(hydroxymethyl)phosphonium chloride, 4% triethanolamine, and 1.0% Triton X- (a wetting agent). The fabric was given two dips and two nips throughrthe solutionand the squeeze rolls of the padder were set to give a tight-squeeze. The fabric was dried for 4 minutes at 80 to 90 C., then cured 5 minutes at 140 C., and finally washed and dried. Itlcontained l5.5%'-resin add-on and 1.5 5% nitrogen, 1.45% phosphorus and 1.23 sulportions of "it were heated ples cured'above C. and containing over-10%" resin-- fur. The fabric was strong and had a good hand. Some of the treated fabric was boiled in a soap-sodium carbonate solution for three hours and some of it was extracted for three hours with tetrachloroethylene. After the alkaline boil, the fabric contained 1.37% nitrogen, 1.25% phosphorus and 0.94% sulfur, while after the organic solvent extraction, it contained 1.54% nitrogen, 1.50% phosphorus and 1.23% sulfur.

EXAMPLE 10 A sample of 8 oz. cotton sateen fabric was padded in an aqueous solution containing 16.5% tris(1-aziridiny1) phosphine sulfide, 16.5% tetrakis(hydroxymethyl)phosphonium chloride, 4% triethanolamine and 1% of a wetting agent and then dried for 4 minutes at 80 to 90 C. The dry fabric was then cut into four pieces and then each piece was cured for five minutes at the temperature shown in Table II. The resin add-on obtained and certain physical data are also shown in Table II. After the fabrics were cured, washed and dried, a portion of each of the four samples was softened with Triton X-400 by padding it through an aqueous suspension of the softener and then drying.

Elmendorf tear strength of untreated control fabric was 11.9 lbs.

EXAMPLE 11 Two fabric treating solutions were prepared as follows: (A) An aqueous solution was made by dissolving 10 parts of tris(1-aziridinyl)phosphine sulfide, 10 parts of tris(hydroxymethyl)phosphine oxide in 80 parts of water and then adjusting the pH of the solution to 7-8 by use of sodium carbonate solution (this solution designated solution A); (B) An aqueous solution was made by dissolving parts of tris(1-aziridinyl)phosphine sulfide, 15 parts of tris(hydroxymethyl)phosphine oxide in 70 parts of water and then adjusting the pH to 6.4 by use of sodium carbonate solution. (this solution designated solution B).

A sample of sateen fabric that was padded in solution A, dried at- 70 C., cured at 150 C. and washed contained 6% resin. Another sample of sateen that was passed through solution B, dried at 70 C., cured at 150 C. and washed contained 6.3% resin. Both fabrics were flame resistant, were strong and had a good hand.

EXAMPLE 12 This example illustrates the influence of varying the mole ratio .of reactants. Seven solutions were made in which the mole ratio of tris(1-aziridinyl) phosphine sulfide to tetrakis (hydroxymethyl)phosphonium chloride was varied from 1:1 to 1:4 and from 4:1 to 1:1 as shown in Table III where tris(l-aziridinyDphosphine sulfide is represented by the term APS and tetrakis(hydroxymcthyl)- phosphonium chloride isrepresented by the term THPC. Each solution contained a total concentration of reagents (APS plus THPC) equal to of the total solution weight. A fabric sample was padded in each of the solutions, dried, cured 5 minutes at 150 C. and then washed and dried. The resin add-on obtained and the Elmendorf tear strength (after softening with a cationic textile softener Triton X-400) are shown in Table III.'-

Table III Moles of Reagent Elmenin Solution Resin dorf Tear Char Length Solution No. Add-on, (warp), (inches) Percent lbs. APB THPO 1 2 4. 4 8. 5 BEL.

1 3 2. 9 7. 3 BEL.

1 4 2. 3 6. 3 BEL.

2 1 7.2 10. 3 BEL (4.9). 3 1 6. 2 10.2 BEL.

4 1 6.6 9.8 BEL (6.5).

1 BEL means sample burned entire length. 2 One of the two samples tested passed the flame test.

The solutions used above were allowed to stand at about 27 C. for 24 hours then again used to treat similar fabric samples. The results obtained with these fabrics were very similar to those described above. This experiment shows that the aqueous solutions are suitable for use even after standing for 24 hours.

EXAMPLE 13 An aqueous solution was prepared containing 17% tris(1-aziridinyl)phosphine sulfide and 17% tetrakis(hydroxymethyl)phosphonium chloride. This solution was used to treat several fabrics by padding, drying, curing and then washing and drying. The fibers used in the fabrics, the resin add-on, and the degree of flame resistance are shown in Table IV. The flame resistance was measured by determining the angle at which a strip of the fabric (5 inches long and A inch wide) would not continue to burn when held in the vertical position and ignited at the bottom and then slowly rotated until the flame went out.

Table IV Flame Resist- Resin ance Strip Test Fabric Treated (Fibers used in Fabric) Add-on, (angle where Percent strip would not support flame),

degrees EXAMPLE 14 A solution was prepared exactly as described in Example 13 except that only 15% of each reagent was used. A sample of wool blanket and a strip of blotter paper were padded in the solution, dried, cured at 150 C. then washed and dried. Both the wool and paper were extremely flame resistant.

We claim:

1. A process for producing a flame-retardant polymer which comprises warming a mixture of (1) an aziridinyl compound selected from the group consisting of a l-aziridinyl phosphine oxide and a l-aziridinyl phosphine sulfide with (2) a methylol phosphorus compound selected from the group consisting of tris (hydroxymethyl) phosphine oxide, tetrakis (hydroxymethyl) phosphonium chloride, and a reaction product of said methylol phosphorus compound with a compound containing at least one trivalent nitrogen atom and at least one member of the group consisting of H and -CH OH attached to a trivalent nitrogen, the proportions of aziridinyl compound to methylol phosphorus compound being such that one aziridinyl group is present for each two methylol groups of the methylol phosphorus compound, and continuing warming of the mixture until said aziridinyl compound and said methylol phosphorus compound 9 have reacted with each other to form a polymeric reaction product.

2. A process for producing a flame-retardant polymer which comprises warming a mixture of (1) an aziridinyl compound selected from the group consisting of tris (laziridinyl) phosphine oxide and tris (l-aziridinyl) phosphine sulfide with (2) a methylol phosphorus compound selected from the group consisting of tris (hydroxymethyl) phosphine oxide, tetrakis (hydroxymethyl) phosphonium chloride, and a reaction product of said methylol phosphorus compound with a compound containing at least one trivalent nitrogen atom and at least one member of the group consisting of H- and -CH OH attached to a trivalent nitrogen atom the proportions of aziridinyl compound to methylol phosphorus compound being such that one aziridinyl group is present for each two methylol groups of the methylol phosphorus compound, and continuing warming of the mixture until said aziridinyl compound and said methylol phosphorus compound have reacted with each other to form a polymeric reaction product.

3. The process of claim 2 wherein the aziridinyl compound is tris (l-aziridinyl) phosphine oxide and the methylol phosphorus compound is tetrakis (hydroxymethyl) phosphonium chloride.

4. The process of claim 2 wherein the aziridinyl compound is tris (l-aziridinyl) phosphine sulfide and the methylol phosphorus compound is tetrakis (hydroxymethyl) phosphonium chloride.

5. The process of claim 2 wherein the aziridinyl compound is tris (l-aziridinyl) phosphine oxide and the methylol phosphorus compound is tris (hydroxymethyl) phosphine oxide.

6. The process of claim 2 wherein the aziridinyl compound is tris (l-aziridinyl) phosphine sulfide and the methylol phosphorus compound is tris (hydroxymethyl) phosphine oxide.

7. A flame-retardant polymer produced by the process of claim 2.

8. A flame-retardant polymer produced by the process of claim 3.

9. A flame-retardant polymer produced by the process of claim 4.

10. A flame-retardant polymer produced by the process of claim 5.

11. A flame-retardant polymer produced by the process of claim 6.

12. A composition for reducing the flammability of fibrous materials which comprises an aqueous solution containing (1) an aziridinyl compound selected from the group consisting of tris (l-aziridinyl) phosphine oxide and tris (l-aziridinyl) phosphine sulfide and (2) a methylol phosphorus compound reactive with said azirir dinyl compound selected from the group consisting of tris (hydroxymethyl) phosphine oxide, tetrakis (hydroxy-' methyl) phosphonium chloride, and a reaction product of said methylol phosphorus compound with a compound containing at least one trivalent nitrogen atom and at least one member of the group consisting of H- and -CH OH attached to a trivalent nitrogen atom, the proportions of aziridinyl compound to methylol phosphorus compound being such that one aziridinyl group is present for each two methylol groups of the methylol phosphorus compound.

References Cited in the file of this patent UNITED STATES PATENTS 2,582,613 Wohnsiedler et a1. Jan. 15, 1952 2,606,901 Parker Aug. 12, 1952 2,654,738 Lecher Oct. 6, 1953 2,660,543 Walter et a1. Nov. 24, 1953 2,666,750 Dickey et a1. Jan. 19, 1954 2,672,459 Kuh Mar. 16, 1954 2,682,521 Coover June 24, 1954 2,772,188 Reeves et a1 Nov. 27, 1956 FOREIGN PATENTS 854,651 Germany Nov. 6, 1952 863,055 Germany Jan. 15, 1953 888,853 Germany Sept. 7, 1953 

1. A PROCESS FOR PRODUCING A FLAME-RETARDANT POLYMER WHICH COMPRISES WARMING A MIXTURE OF (1) AN AZIRIDINYL COMPOUND SELECTED FROM THE GROUP CONSISTING OF A 1-AZIRIDINYL PHOSPHINE OXIDE AND A 1-AZIRIDINYL PHOSPHINE SULFIDE WITH (2) A METHYLOL PHOSPHORUS COMPOUND SELECTED FROM THE GROUP CONSISTING OF TRIS (HYDROXYMETHYL) PHOSPHINE OXIDE, TETRAKIS (HYDROXYMETHYL) PHOSPHONIUM CHLORIDE, AND A REACTION PRODUCT OF SAID METHYLOL, PHOSPHORUS COMPOUND WITH A COMPOUND CONTAINING AT LEAST ONE TRIVALENT NITROGEN, ATOM AND AT LEAST ONE MEMBER OF THE GROUP CONSISTING OF H-AND-CH2OH ATTACHED TO A TRIVALENT NITROGEN, THE PROPORTIONS OF AZIRIDINYL COMPOUND TO METHYLOL PHOSPHORUS COMPOUND BEING SUCH THAT ONE AZIRIDINYL GROUP IS PRESENT FOR EACH TWO METHYLOL GROUPS OF THE METHYLOL PHOSPHORUS COMPOUND, AND CONTINUING WARMING OF THE MIXTURE UNTIL SAID AZIRIDINYL COMPOUND AND SAID MTHYLOL PHOSPHORUS COMPOUND HAVE REACTED WITH EACH OTHER TO FORM A POLYMERIC REACTION PRODUCT. 